Hydroperoxides

ABSTRACT

Bicyclic triolefins are converted to peroxides, alcohols and ketones.

United States Patent Solomon July 29, 1975 HYDROPEROXIDES [58] Field of Search 260/610 R, 610 B, 618 C, [75] Inventor: Paul W. Solomon, Bartlesville, Okla. 260/632 586 617 R; 509/624 [73] Assignee: Phillips Petroleum Company, [56] Reierences Cited Bartlesvllle, Okla. 22 F1 A 24 3 UNITED STATES PATENTS 1 2,776,953 1/1959 Taves 260/82.5 [21] App]. No.2 354,094 3,763,240 10/1973 Solomon 260/586 R RltdU.S.A l' t' Dt c t, t js M h 18 Primary Examiner-Bernard Helfin on lnua ion-m-par 0 er. 0. arc

1968, Pat. No. 3,763,240, which is a Exammer continuation-in-part of Ser. No. 509,624, Nov. 24,

i965, abandoned. [57] ABSTRACT Bicyclic triolefins are converted to peroxides, alcohols [52] US. Cl...... 260/610 R, 260/586 B, 260/6l7 R, and tones 252/522; 424/331; 260/486 R Int. Cl. C07c 73/06 4 Claims, No Drawings HYDROPEROXIDES This application is a continuation-in-part of US. application Ser. No. 714,070, filed Mar. 18, 1968, now US. Pat. No. 3,763,240, which is a continuation-inpart of US. application Ser. No. 509,624, filed Nov. 24, 1965, now abandoned.

This invention relates to a process for the production of novel triolefin hydroperoxides. In one aspect it relates to the production of l,2-bis(3-cyclohexenlyl)ethylene hydroperoxides. In another aspect it relates to the production of alcohols through the reduction of said triolefin hydroperoxides. In another aspect it relates to novel ketone derivatives of said triolefin hydroperoxides.

In a commonly assigned copending case (U.S. application Ser. No. 502,544, filed Oct. 22, 1965, now abandoned, and its continuation-in-part application Ser. No. 665,239, filed Sept. 5, 1967, now US. Pat. No. 3,463,828, issued Aug. 26, 1969), there is described a method for the preparation of novel triolefin compounds.

It is therefore an object of this invention to prepare novel triolefin hydroperoxide derivatives of said novel compounds produced in the above-identified application.

It is another object of this invention to provide a process for the production of novel alcohol derivatives of said triolefin compounds produced in the aboveidentified application.

It is another object of this invention to provide a process for the production of novel ketone derivatives of said triolefin compounds produced in the aboveidentified application.

It is yet another object of this invention to provide novel 1,2-bis(3-cyclohexen-1yl)ethylene hydroperoxides.

It is another object of this invention to provide novel alcohol derivatives of l,2-bis(3-cyclohexen-lyl)ethylene hydroperoxides.

It is still a further object of this invention to provide novel ketone derivatives of l,2-bis(3-cyclohexen-lyl)ethylene hydroperoxides.

Other objects and many of the attendant advantages of this invention will be readily appreciated as the same becomes better understood by reference to the following detailed description.

I have now discovered a process for the production of novel triolefin hydroperoxides, said process comprising the step of oxidizing a triolefin characterized by the following formula:

1! RR R R RR R -C C- .R

RRRR RRRR wherein R is selected from the group consisting of hydrogen, methyl and ethyl, wherein the total number of carbon atoms in all of said R groups does not exceed 8, and wherein at least one of said R groups which is in a position allylic to an olefinic double bond is hydrogen, with an oxygen-containing gas.

Specific examples of triolefins which are useful as the starting materials in the practice of this invention are as follows:

1,2-bis( 3-cylcohexenl -yl)ethylene 1,2-bis( l-methyl-3-cyclohexenl -yl)ethylene 1,2-bis(2-methyl-3-cyclohexen-1-yl)ethylene I ,2-bis( 3-ethyl-3-cyclohexenl yl)ethylene l,2-bis(4-methyl-3-cyclohexenl-yl)ethylene I ,2-bis(5-ethyl-3-cyclohexen-1-yl)ethylene l ,2-bis(6,6-dimethyl-3-cyclohexen-1-yl)ethylene 3 ,4-bis( 3-cyclohexenl -yl )-3-hexene I ,2-bis(2,6-dimethyl-3-cyclohexen-1-yl)ethylene 2,3-bis(3-methyl-3-cyclohexen-1-y1)-2-butene l,2-bis( l,3-dimethyl-3-cyclohexenl -yl)ethylene 2,3-bis(4-methyl-3-cyclohexen-1-yl)-2-butene 1,2-bis( l,4-dimethyI-3-cyclohexen-1-yl)ethy1ene 1,2-bis(5,6-dimethyI-3-cyclohexen-1-yl)ethylene 2,3-bis( 1,3,4-trimethyl-3-cyclohexenl -yl)-2-butene I,2-bis( 2,5,6-trimethyl-3-cyclohexenl -yl )ethylene 1,2-bis(2,6diethyl-3-cyclohexenl -yl )ethylene 3,4-bis( 4-ethyl-3-cyclohexenl -yl)-3-hexene l-( 3-methyl-3-cyclohexenl -yl )-2-( 2-methyl-6-ethyl- 3-cyclohexenl -yl )ethylene 1-(3-cyc1ohexen-l-yl)-2-(2-methyl-3-cyclohexen-1- yl )ethylene.

The oxygen-containing gas can be selected from the group consisting of pure oxygen, a mixture of oxygen and an inert gaseous diluent such as nitrogen, air, and air .enriched' with oxygen. The gas is conveniently passed into the triolefin, preferably with good dispersion through stirring or other means of agitation, at a rate equal to or in excess of the rate at which the oxygen is consumed. It is generally desirable that the flow of oxygen-containing gas be discontinued, and the oxidation terminated, when not more than about 30 per cent of the triolefin has been oxidized in order to obtain maximum selectivity to monohydroperoxide products.

Although the temperature at which the oxidation is carried out can be varied over a wide range, the temperature will usually be within the range of about 20 to 200C, generally being within the range of about 40 to C. The higher temperatures provide a faster rate of reaction whereas the lower temperatures result in greater selectivity to monohydroperoxide product. The reaction time usually will be within the range of about 10 minutes to about 24 hours, generally being within the range of about 30 minutes to about 6 hours. If desired, a solvent, e.g. benzene, inert under the reaction conditions, can be used. The reaction pressure need be only sufficient to maintain the triolefin and/or solvent in substantially the liquid phase.

It is also within the scope of this invention that an initiator can be employed in the oxidation step in order to decrease the initial induction period during which hydroperoxide formation is relatively slow. Any of the initiators which are generally useful in the production of hydroperoxides can be employed. Examples of some suitable initiators are chemical initiators such as peroxides, hydroperoxides, and azobiisobutyronitrile; ultraviolet light; and metal-containing compounds such as cobalt naphthenate, cupric oxide, and the like.

The hydroperoxides produced in accordance with the above-identified process have the following generic formulas:

wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein the total number of carbon atoms in all of said R groups does not exceed eight.

Specific examples of unsaturated ketones arc:

l-(3-cyclohexen-l-yl)-2-(2-oxo-3-cyclohexen-lyl)ethylene l-(3-cyclohexen-l-yl)-2-(5-oxo-3-cyclohexen-1- yl)ethylene 1-(3-cyclohexen-1-yl)-2-(4-oxo-2-cyclohexen-lyl)ethylene cyclohexenylidene)ethane l-( l-methyl-3-cyclohexen-l-yl)-2-( l-methyl-S-oxo- 3-cyclohexen-l-yl)ethylene 1-(4-methyl-3-cyclohexen-l-yl)-2-(4-methyl-2-oxo- 3-cyclohexen-l-yl)ethylene 1-(6,6-dimethyl-3-cyclohexen-l-yl)-2-(6,6-dimethyl- 2-oxo-3-cyclohexen-l-yl)ethylene 3-(3-cyclohexene-l-yl)-4-(5-oxo3-cyclohexen-1- yl)-3-hexene l-(l,3-dimethyl-3-cyclohexen-1-yl)-2-(1,3-dimethyl- 5-oxo-3-cyclohexen-l-yl)ethylene l-(l,4-dimethyl-3-cyclohexen-1-yl)-2-(1,4-dimethyl- 2-oxo-3-cyclohexen-l-yl)ethylene 2-(1,3,4-trimethyl-3-cyclohexen-1-yl)-3-(1,3,4- trin. thyl-5-oxo-3-cyclohexen-l-yl)-2-butene 3-(4-ethyl-3-cyclohexen-l-yl)-4-(4-ethyl-5-oxo-3- cyclohexen-l-yl)-3-hexene (2-methyl-5ethyl-3-cyclohexen-1-yl)-2-(6-methyl- 4-oxo-2-cyclohexen-l-yl)ethylene 1-(3-cyclohexen-l-yl)-2-(4-methyl-2-oxo-3- cyclohexen-1-yl)ethylene l-(3-methyl-3-cyclohexen-1-yl)-2-(3-methyl-4-oxo- 2-cyclohexen-l-yl)ethylene l-oxo-l-(2,6-diethyl-3-cyclohexen-l-yl)-2-(2,6-

diethyl-3-cyclohexenylidene)ethane.

The ketones produced according to the process as described hereinabove have a pleasant roselike odor and can be utilized as rose-odor additives. These ketones can also be used in the preparation of compounds for agricultural use. The unsaturated ketones of this invention can be hydrogenated in a known manner (Chemical Abstracts, Vol. 51, column 244d, 1957) to yield the saturated ketone and the saturated ketone can be sprayed onto soil as an effective soil fungicide. For example, the 1-(3-cyclohexen-l-yl)-2-(5-oxo-3- cyclohexen-1-yl)ethylene of Example V hereinafter can be formed into the corresponding saturated ketone, i.e., 3-(2-cyclohexylethyl)cyclohexanone, and when this saturated ketone was sprayed in the amount of 48 pounds of ketone per acre onto soil infested with Rhizoclonia solani fungus, the fungus was sufficiently killed to allow a major amount of seeds in the soil, e.g., pea seeds (Pisum sativum L. var. Perfection), to germinate and grow into healthy plants, see Example VI hereinafter.

The unsaturated alcohols of this invention can be used in a number of applications which involve one or more of the olefinic double bonds and/or hydroxyl groups. For example, acrylic acid or methacrylic acid can be esterified with the unsaturated alcohols and the esters thus produced can be polymerized to yield polymers having a greater number of cross linkages than occur in the usual polyacrylate or polymethacrylate resins. Additionally, the esterified unsaturated alcohols can be used as plasticizers for synthetic resins such polyethylene or polyvinyl chloride.

The following examples describing specific embodiments of this invention are given by way, of illustration only, and obviously may be modified considerably as to catalyst employed, operating conditions, and quantitative relationships, without departing from the spirit and scope of the invention.

EXAMPLE I A stream of oxygen was passed for 2 hours into 230 g. of trans-l,2-bis-(3-cyclohexen-l-yllethylene (88 weight per cent purity) containing 20 g. of cupric oxide (freshly ground in vacuo in a ball mill) at 65-67C with vigorous stirring. The rate of oxygen consumption increased as the reaction progressed, being practically nil initially and increasing to 20 ml/min. at the end of 1 hour, 43 ml/min. at the end of 1V2 hours, 51 ml/min. at the end of 1% hours, and 57 ml/min. at the end of 2 hours. At the end of the 2-hour reaction period, during which time 0.12 mol of oxygen was consumed, the mixture was filtered hot through an 0.8 micron millipore filter to remove the cupric oxide from the light yellow solution. Analysis of the filtrate by the method of Siggia, Quantitative Organic Analysis via Functional Groups, 2nd Edition, John Wiley and Sons, Inc. New York (1954), p. 150, showed the presence of 0.077 mol of hydroperoxides, rerpresenting a 64 mol per cent yield based on the oxygen consumed. The solution of hydroperoxides was refluxed for 30 minutes with a solution of 25 g. (0.2 mol) of sodium sulfite in 200 ml of water to reduced the hydroperoxides to the corresponding alcohols. Approximately two-thirds of the hydrocarbon layer was separated from the aqueous layer, washed three times with water, and dried over magnesium sulfate. After removal of unreacted triolefin from the dried solution, the product was distilled to give 4.1 g ofa fraction boiling at lO5l08C/O.l3 mm and 1.1 g. ofa second fraction boiling at lO8-l20C/O. 1 3 mm; 2.3 g. of resinous material remained as a residue.

The following analysis of the fraction boiling at l08C/0.l3 mm Hg was carried out to establish the identity of the product. Nuclear magnetic resonance analysis of the fraction gave results consistent with those to be expected for a mixture of l,2-bis(3- cyclohexen-l-yl)ethylene having a single hyroxyl group in a position allylic to an olefinicfdouble bond. The results are summarized in Table l.

V TABLEI Proton Distrihution* H11 HI) H( II HI Found 5,6 1.0 0.9 12.5 Theory 6 l l 12 *Designations for proton type are as follows:

H" cyclic non-terminal olefinic protons H" non-cyclic non-terminal olcfinic protons H" hydroxyl protons H" protons on carbons attached to hydroxyl groups H" all other protons Elemental analysis of the fraction showed the weight per cent of carbon and hydrogen to be 82.2 and 9.8. respectively, compared with calculated values of 82.3 and 9.8, respectively, for a mixture of l,2-bis(3- 1 (4-hydroperoxy-2-cyclohexenl -yl)ethylene, hydroperoxy-1-(3-cyclohexen-l-yl)-2-(3- cyclohexenylidene )ethane.

and 1- EXAMPLE III cyclohexen-l-yl)-ethylenes having a single hydroxyl 5' group in a position allylic to an olefinic double bond. The molecular weight, by osmometry, of this fraction The product obtained in Example ll, product A, was was 203, compared with a calculated value of 204 for divided into five equal parts and each part selectively the above mixture of hydroxy compounds. The molecuhydrogenated according to the following procedure. lar weight by mass spectrometer analysis was 204. In- One hundred and thre gram was di l d i 100 l frared analysis of the fraction indicated the degree of of ethanol and placed in a Brown hydrogenator with olefinic unsaturation to be approximately the same as 14 gram f palladium catalyst i d with lead In that of the triolefin reactant. Strong absorption at 2.9 three f the runs 0'Q5 O 4 gram f quinoline was and microns indicated the Preset:e of secohdhry added in order to make the hydrogenation more selechydroxyl groups. A small amount of substance conta l5 tive for hydroperoxide over olefinic unsaturation. Howmg a Carbonyl gtOuP Conlugated wlth t Olefimc ever, the hydrogenation rate was poor when quinoline ble bond was indicated by weak absorption at 5.95 miwas present Therefore, no quinoline was used in the Hons final two runs and the hydrogenation was stopped slightly past the hydrogen uptake value for total EXAMPLE n OOH reduction. The five products from these hydrogenations contained only 3 to 5 weight per cent 1.2- Five hundred grams (2.66 mole) of l2 biS(3 bis(3-cyclohexen-1-yl)ethylene hydroperoxides by cyclohexen-lyl)ethylene (BCE) was placed in a three- AS203 mranon necked, l-liter Morton flask equipped with condenser, The five products were combmed' filtered to remove thermometer and hollow Truebore stirrer and heated catalyst and Solvents were evapfrated m vacuum a to about 65C. With vigorous stirring a metered stream rotatmg evaporzftorj The combined pioducts we'ghed of oxygen was passed into the triolefin, and the off 492 i Addmg l h 13 grams much was used for gases from the condenser were passed through a dry ice analytical purposes indicated that a total of 505 grams trap and a wet-test meter. Oxygen flow was regulated of Product was Produced Approximately 8 grams such that a positive pressure was maintained in the sys- (0-24 mol) of 2 was lost y reduction that the tem Aft approximatdy 4 hours, a granular, Sticky tual amount of product expected would have been 507 solid began precipitating on the flask walls. The reacgtams- TWO grams of Suspended Solid was removed tion was terminated after 6V2 hours. At this time 15140 from the Product y filtration and the resulting material ml (0.62 mol) of oxygen had been Consumed Th (490 grams) fractionated on an 18-inch glass helices product, a light yellow liquid, was filtered to remov packed column at 0.2-0.6 mm pressure and a 5:1 reflux the suspended granular material. The granular material ratio. Cuts were analyzed by boiling point, refractive adhering to the flask walls was washed with n-pentane index, GLC and GLC/mass combination to give the folas was that on the filter paper. The solvent was evapolowing approximate analysis:

Grams Grams Grams Fraction Grams Dihydro Mono- High Boiling Point, "C n Grams BCE BCE* PIZSIZCS Boiler 78-83 1.5096l.5099 331 314 17 83-165 1.5100-15328 130 53 1 71 5 165-200 9 9 Residue 15 15 Total 485 367 18 71 29 Fractionation Loss 5 Mass/GLC combination characterized this material which occurs as a single peak cluting before rated and the recovered additional liquid added to the main filtrate. The precipitate weighed 2.0 grams and the filtrate weighed 515 grams.

Titration of the liquid product with AS203 gave a hydroperoxide content of 20.4 i 0.3 weight percent calculated as monohydroperoxy-substituted 1,2-bis(3- cyclohexen-l-yl)ethy1ene, or 0.48 mol. Only after a trace of liquid product was recovered from the dry ice trap in the exit gas line. The hydroperoxide product comprised a mixture of l-(3-cyclohexen-1-yl) 2-(1 hydroperoxy-3-cyclohexen-l-yl)ethylene, 1-(3- cyclohexen-l-yl)-2-(2-hydroperoxy-3cyc1ohexen-1- yl)ethylene, l-(3-cyclohexen-l-yl)-2-(5-hydroperoxy- 3-cyclohexen-l-yl)ethylene, l-(3-cyclohexen-l-yl)-2- Selectivity of the hydrogenation for hydroperoxide over olefinic double bonds was fair even though quinoline was not used.

If the 13 grams of material used for analytical determinations for hydroperoxide is distributed as above and the 2 portions of precipitated material (4 grams) removed by filtration are considered as High Boiler and the loss due to fractionation is added back proportionately, the following distribution is obtained:

Grams BCE Dihydro-BCE 400 Mono-oxy Products 74 High Boiler 33 Total 507 Therefore, olefin conversion was 20 per cent of the OX- ygenated products obtained, 67 per cent were monooxy products comprising alcohols and ketones.

Specifically, Fraction B comprised a mixture of major amounts of olefinically unsaturated alcohols, 1- (3-cyclohexen-1yl)-2-( 1-hydroxy-3-cyclohexenlyl)ethylene, l-(3-cyclohexen-l-yl)-2-(2-hydroxy-3- cyclohexen-l-yl)ethylene, l-(3-cyclohexen-l-yl)-2-(5- hydroxy-3-cyclohexen-1-yl)ethylene, l-( 3-cyclohexenl-yl)-2-(4-hydroxy-2-cyclohexen-1-yl)ethylene, and l-hydroxy-l-(3-cyclohexen-l-yl)-2-(3- cyclohexenylidene)ethane, and minor amounts of olefinically unsaturated ketones, l-(3-cyclohexen-l-yl)-2- (2-oxo-3-cyclohexen-l-yl)ethylene, 1-(3-cyclohexen- 1-yl)-2-(5-oxo-3-cyclohexen-l-yl)ethylene, l-(3- cyclohexen-l-yl)-2-(4-oxo-2-cyclohexen-1- yl)ethylene, and l-oxo-l-(3-cyclohexen-1-yl)-2-(3- cyclohexenylidene)ethane.

The mixture comprising Fraction B was converted entirely to the saturated ketones and compared with a mixture of the same saturated ketones which had been individually prepared by another method and authenticated by various types of analysis. Comparisons of the two mixtures by Thin Layer Chromatography and Gas Liquid Chromatography established that the mixtures contained the same compounds.

EXAMPLE 1V Thirty-nine grams of the mono-oxy product of Example lll (approximately 0.1 mol of oxygenated product) was dissolved in 100 ml of commercial dry ether and dropped into a stirred solution of 5.7 grams (0.15 mole) of lithium aluminum hydride dissolved in 150 ml of ether held at 25C in a 3-neck flask equipped with condenser, dropping funnel and Truebore stirrer. Reaction was mild indicating very little carbonyl compound was present. After the addition of the product from Example "I, stirring was continued for 30 minutes. The mixture was poured into 1 liter of ice-water containing 100 ml of H 80 After decomposition of the complex, the aqueous phase was extracted 3 times with ether, the ether phases combined and washed with H and saturated Nal-lCO solution, and the ether evaporated to yield 39.2 grams of yellow oil. This oil was dissolved in a small amount of cyclohexane and chromatographed on 800 grams of alumina with cyclohexane, then methanol as eluants. After removal of the solvents in vacuo on a rotating evaporator, 17.2 grams of material was recovered from the cyclohexane solution which analyzed as slightly hydrogenated l,2-bis(3- cyclohexen-l-yl)ethylene by infrared. Twenty-one grams of material was recovered from the methanol solution which was distilled to give two fractions-C-b.p.- 122l 36C/1 mm weighing 18.7 g., n -l .5242, water white, and D-b.p.-l27l40C/0.l mm weighing 1.4 g., yellow, very viscous,-and 0.5 g. of residue.

The following analytical data were obtained for C, which comprised a mixture of the isomeric alcohols l- (3-cyclohexen-1yl)-2-(1-hydroxy-3-cyclohexen-lyl)ethylene, l-(3-cyclohexen-l-yl)-22-hydroxy-3- cyclohexen-l-yl)ethylene, l-(3-cyclohexen-l-yl)-2-(5- hydroxy-3-cyclohexen-l-yl)ethylene, l-(3-cyclohexenl-yl)-2-(4-hydroxy-2-cyclohexen-l-yl)ethylene, and l-hydroxy-l-(3-cyclohexen-l-yl)-2-(3- cyclohexenylidene)ethane.

Theory Found "/1 C 82.3 8 l .9 '7 H 9.8 9.8 Osmometric Molecular Weight 204 203 Type of Protons Number of Protons Theory Found Cyclic Olefinic 4.0 3.7 Ethylenic 2.0 1.6 --OH Protons 1.0 1.1 Protons alpha to OH 0.7 Other Protons 13.0 12.9

The slightly low olefinic proton values are indicative of the partial nonselectivity of the hydroperoxide hydrogenation. The ratio Protons alpha to -OH/-OH Protons indicates a ratio of 7/4 for secondary/tertiary alcohols.

EXAMPLE V The product of Example IV was oxidized according to the following procedure. Ten and Two-tenths grams (0.05 mol) of the product was dissolved in 10 ml of acetone and a solution of 3.0 grams (0.03 mol) of CrO and 2.5 ml of 11 50 in 9 ml of water was slowly added with stirring, keeping the temperature at 5-10C by means of an ice bath. The solution was dark blue-green after all of the CrO solution was added. It was immediately diluted with an equal volume of H 0, ether extracted 3 times, the combined either phases washed with water and saturated NaHCO solution, and the ether evaporated to give 10.] grams of oil. Distillation of the oil gave two fractions-E-bp-l l9l32C/l .0 mm weighing 8.1 g., n -1.5246, fruity-odored, pale yellow, and F b.p. 132C/1.0 mm weighing 0.4 g. The pot residue weighed 0.5 g.

Analytical data were obtained on E, which comprised a mixture of the tertiary alcohol l-(3-cyclohexenl-yl)- 2-( 1-hydroxy-3-cyclohexen-l-yl)ethylene and the ketones l-(3-cyclohexen-l-yl)-2-(2-oxo-3-cyclohexen-lyl)ethylene, l-(3-cyclohexen-l-yl)-2-(5-oxo-3- cyclohexen-1-yl)ethylene, l-(3-cyclohexen-l-yl)-2-(4- oxo-2-cyclohexenl -y] )ethylene, and l-oxo- 1 3- cyclohexen- 1 -yl )-2( 3-cyclohexenylidene )ethane.

Calculated as containing 36 per cent ten-alcohol and 64 per cent mixed ketones, as would be expected from the 7/4 secondary/tertiary alcohol ratio in C.

"/4 Protons Proton Type Theory Found Aromatic 2.7 2.9 Olefinic" 28.7 24.7 Protons from OH 2.l 2.1 Other protons 66.5 70.3

" Both cyclic olcfinic and ethylenic protons present;

peaks overlap. Figured on the basis of percent 3-(2-phenylethyl)- cyclohexanone, 40 percent and 50 percent mixed oxo-substituted derivatives of 1,2- bis( 3-cyclohexenl -yl )cthylene.

EXAMPLE VI The ketone 3-( 2-cyclohexylethyl)cyclohexanone,

The infested soil was then transferred to 4-inch vacuum-formed plastic pots, and 25 pea seeds (Pisum sativum L. var. Perfection) were placed in a one-half inch depth, one pea seed in each pot.

The soil in each pot was then drenched with 25 milliliters of a liquid which contained 0.15 milliliter of the ketone, 4 milliliters of acetone, 2 milliliters of TRI- TON X-l (0.5 weight per cent TRITON X-155 in water by volume) and 94 milliliters of distilled water. This amount of the ketone-containing liquid was equivalent to a concentration of active ketone of 48 pounds per acre.

After a period of 14 to 18 days, the 25 pots were observed and 80 per cent contained viable plants thereby indicating that in 80 per cent of the cases where the solution of the ketone was used, the fungus was sufficiently killed to allow. the pea seed to germinate and a healthy plant grow therefrom. The concentration of fungus in the soil of each pot was sufficient, absent the application of the ketone solution, to prevent the growth of a plant from any of the 25 test seeds.

Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.

I claim:

1. Hydroperoxides characterized by the following which is the saturated ketone that corresponds to l-(3- 30 formulas:

OH R RR RR R RRo RRR R R RR I Y Y I.

R- -c=c R R- -c=c- R RORR R RRR R RR RRRR on R RR R R RR R R RR H00 I i =.R R- C=C .R l R R R ROH R RR RR RRRR RR R RRR

R- CC OOH RRRR

cyclohexen-l-yl)-2-(5-oxo-3-cyclohexen-l-yl)ethylene wherein R is selected from the group consisting of hyof Example V hereinabove, was used in a soil fungicide test.

In the test, lOOO grams of autoclaved soil was mixed with 50 grams of a cornmeal-sand-water (weight ratios of 7/6/5, respectively) mixture which was infested with Rhizoctonia sulani in a plastic bag.

drogen, methyl and ethyl and wherein the total number of carbon atoms in all of said R groups does not exceed eight.

2. A novel hydroperoxide as defined in claim 1 selected from the group consisting of l-(3-cyclohexen-lyl)-2-(l-hydroperoxy-3-cyclohexen-l-yl)-ethylene, l-

RRR RR R v 1 R- C=C R RORR RRRR 16 wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein the total number of carbon atoms in all of said R groups does not exceed eight.

4. A novel hydroperoxide as defined in claim 1 which is l-(3-cycIohexen-l-yl)-2-(5-hydroperoxy'3- eyclohexenl -yl )-ethylene. 

1. HYDROPEROXIDES CHARACTERIZED BY THE FOLLOWING FORMULAS:
 2. A novel hydroperoxide as defined in claim 1 selected from the group consisting of 1-(3-cyclohexen-1-yl)-2-(1-hydroperoxy-3-cyclohexen-1-yl)-ethYlene, 1-(3-cyclohexen-1-yl)-2-(2-hydroperoxy-3-cyclohexen-1-yl)ethylene, 1-hydroperoxy-1-(3-cyclohexen-1-yl)-2-(3-cyclohexenylidene)ethane, 1-(3-cyclohexen-1-yl)-2-(5-hydroperoxy-3-cyclohexen-1-yl)-ethylene and 1-(3-cyclohexen-1-yl)-2-(4-hydroperoxy-2-cyclohexen-1-yl)ethylene.
 3. Hydroperoxides characterized by the following formula:
 4. A novel hydroperoxide as defined in claim 1 which is 1-(3-cyclohexen-1-yl)-2-(5-hydroperoxy-3-cyclohexen-1-yl)-ethylene. 